Ricinoleic acid ester of triethanolamine



Patented Jan. 14, 1941 2,228,985 RICINOLEIC ACID ESTER. on ramrmuon- ALHNE Melvin De Groote, University City, and Bernhard Kelser and Charles Melvin Blair, In, Wchstcr Groves, Mm, asslgnors, lay mesne assignments, to Petrolite florporation, Ltd a corporation or Delaware No Drawing.

Application December 21, ldt'l,

r Claims.

".lhh intention relates to new products adapted ior use as wetting, dispersing or emulsifying openl it relates more particularly to new prod:- ucts ohtaincd hy the partial esteriflcation oi tri- W ethonolamine hy rlcinoleic acid, that is, to the mono and di-ricinoleic acid esters oi triethanolae, and to-mlxtures thereoi; and it includes not only the new products, hut also a new process :lor their production. The new products m at the invention are very stahle, and highly edec tire, in acid solution.

it has heretofore heen proposed to prepare condensation products at higher latty acids, such as stearic acid, etc, with alkylolamines, including primary, secondary and tertiary amines, hy heatinr mirtures oi the iatty acids and the alohamines totemperatures in the neighborhood at ltd i3. huch proposed processes in tact result in the production oi complex mixtures containina ht hath the simple salt or soap oi the iatty acid with the shrine and esters oi the allrylolamine with the iatty acid, and, where primary or second ary amines are used, the mixtures also contain amides or esters amides oi these hicher iatty up acids and the amines. Apparently in such procasses, the iatty acid initially reacts with the amine, particularly when tertiary amines are med, hr simple addition, with the lormation oi the soap or salt, which product is suhseouentiy m conrerted in part into the ester upon heatiny at the relatlrely high temperatures, hy rearrancement with elimination or water. Nevertheless, in the product hnally produced, there has always hcen present, so tar as we have been aide to deti termine, a suhstantial amount or the soap or salt at the amine and the fatty acid, the condensation to term the ester always being incomplete. While such proposed processes may he used with some decree oi success With such iatty acids as stearic m acid, and result in the production oi mixtures oi esters and salts oi" the aliqllolamines, the monoand dl-ricinoieic acid esters oi trlethanolamine cannot he produced hy such a process hecause the ricinoleic acid, when heated to such high temperaill trues, polymer-ices with more or less rapidity, so that the product obtained is a. polymerized ricinolelc acid, rather than the desired ester or esters. the near products produced in accordance with no the present invention may he represented by the yraphic iormula:

. noolm ltOOiHr-N HDChHo (or coo-no in which one oi the his may represent the chain Crzl-lnOHCO characteristic oi rlcinoleic acid, and the other hydrogen, or hoth may represent the chain CmHasOHCU In accordance with the present invention, these a new products are produced hy aicoholysis loy heatinc toeether, in proper proportions, castor oil or other ester of ricinoieic acid and triethanolaimine, it it is desired to produce a product which contains predominantly the mono-esten'd moles oi yo triethanoiane should he used tor each mole of castor oil; While it it is desired to produce a product contalmne' predominantly the cit-ester, about 3 moles oi triethanolae should he used tor each 2 moles of castor oil. it will he under- 15 stood that, as in all organic reactions, the yields oi the desired products are not uuantitatiye and the products obtained, urhile containing a mayor and predominating proportion oi the desired ester, will necessarily contain smaller proportions of so other esters oi triethanolamine and ricmoleic acid as Well as unreacted starting material, etc. For erample, ii triethanolamine and castor oil are reacted in the proportions oi ahout 3 moles oi triethanolane to l mole of castor oil, tor the as production at the mono-ricinolelc acid ester oi triethanolamine, the product ohtained will contain a major and predoatinc proportion at this compound, hut it also contain relatively small amounts at the di-ricinoleic acid estenthc trl-ricinoleic acid ester, as Well as unreactcd castor oil, triethanolamine, etc. it esters oi ricinoleic acid other than castor oil, ior example, ricinoleic ethyl ester, he used, the molar ratios at the trlethanolamine and the ester pill, at 35 course, he erent than tor castor oil, hut will he such that for each mole oi triethanolamine there is used an amount oi ester equivalent to from shoot 1 to shout d moles oi ricinoleic acid:

The h BW products oi the present invention are advantaceously produced in neutralized iorm, hy neutralizing the reaction product with suitahie acids, such as acetic acid, which iorm salts with the esterided amine. Tertiary ones iorm salts with acids lay a simple additiye reaction, and such salts may he tormed directly hy the addition of the proper amount oi the acid to the anhydrous reaction mixture, or, it desired, the reaction product obtained may he dissolved in an acidu lated aqueous solution, in which it dissolves or dis 5d perses to term clear solutions or dispersions,

e new products are insoluhle in hydrocarhon solvents. They dider irorn orary netting, disper-sing or emulsifying agents in that the suriaceactive ion is the cation, and not the anion, dash to materials as soaps, Turkey red oils, sulionic acids, sulfonated alcohols, etc., which are wetting, dispersing or emulsifying agents. have, as their surface-active ion, the anion. The new products 8 are, accordingly, highly stable and eii'ective in acid solutions.

In i'orming the-new products, as pointed out above, castor oil and triethanolamine, in selected proportions, are heated together to temperatures 10 in excess of 100 0., but below the temperature at which decomposition might take place. Ad-

- vantageously, the mixture is heated to a temperature between about 150 C. and about 180 C. for, a suiilcient length of time to permit the reaction to goto substantial completion, for ex- :ample, for about two hours, the reaction proceeding smoothly and readily, and yielding a reaction product in the form of a yellow oil. In this product, there is present not only the desired esters, but also the glycerin set free in the reaction. For many purposes, the presence oi glycerin in the final product is unobiectionable as there is no necessity for its removal if the product is intended for such purposes; On the other hand, ii. desired, the glycerin is readily removed as by washing with a suitable salt solution.

The invention will be further illustrated by the following specific example, but it is not limited thereto.

Emample.-930 parts of castor oil and 4220 par oi triethanolamine are heated to a temperature between about 150 C. and 180 C. for about two hours. The product obtained, when cooled, is a' yellow oil. 216 parts of acetic acid are added to the product to neutralize it. The product so obtained consists predominantly of the acetate of mono-ricinoleic acid ester 6! triethanolamine,

I represented by the graphic iormula: CiIHliOHOOOOIHl noolm rtcrnooon Hooim It, in the process of the above example, the" ester, and the tri-ester. Furthermore, it will be understood that the triethanolamine used is a commercial product, and as such is not pure triethanolamine, but contains relatively small amounts of mono! and di-ethanolamine, ethanol- 5 ethylamines, and other alkylol or alkylol alkyl- .arnines, all of which to some extent enter the reaction and result in the production of corresponding esters in the final product, even though these esters are present but to a minor in extent.

The products obtained may be used in the form of the free base, that is, the tree amine, but are advantageously neutralized by the additionof an acid, or dissolved in aqueous acid to II form a dispersion or solutiontherein. In the example, the acetate has been specifically described, but it will be understood that instead 01' acetic acid, the product may be neutralized with other organic acids, such as propionic acid, 20

butyric-acid, lactic acid, by inorganic acids, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or other inorganic acid, or by higher fatty acids, such as ricinol'eic acid, or other higher fatty acids with the formation of 25 the correspondingsalts. In this specification and the appended claims, the term ester oi triethanolamine" is used to designate not only esters inthe form 01 the free bases, but also their salts or neutralized derivatives. 510

We claim:

1. Products of the class consisting of the monoricinoleic acid ester of triethanolamine and the di-ricinoleic acid ester of triethanolamine.

2. The mono-ricinoleic acid ester of trlethanolamine.

' ,3. The di-ricinoleic acid ester of tr'iethanolamine.

4. The process of preparing the mono-ricinolelc acid ester oi triethanolamine which com- 40 prises heating castor oil and triethanolamine in the molecular proportions of about 3 moles of triethanolamine to 1 mole of castor oil to a temperature in excess of C. for a suiilcient period of time to permit substantial esteriflcation 46 of the triethanolamine.

' MELVIN DE GROO'IE.

BERNHARD KEISER. CHARLES BLAIR, JR. 

